CN1826175A - Process for regenerating a spent sorbent - Google Patents
Process for regenerating a spent sorbent Download PDFInfo
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- CN1826175A CN1826175A CNA2004800177044A CN200480017704A CN1826175A CN 1826175 A CN1826175 A CN 1826175A CN A2004800177044 A CNA2004800177044 A CN A2004800177044A CN 200480017704 A CN200480017704 A CN 200480017704A CN 1826175 A CN1826175 A CN 1826175A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3416—Regenerating or reactivating of sorbents or filter aids comprising free carbon, e.g. activated carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
- B01J20/3475—Regenerating or reactivating using a particular desorbing compound or mixture in the liquid phase
Abstract
A method and apparatus is provided for regenerating a sorbent that h as been poisoned by components derived from flue gas. The sorbent is treated wi th an agent to remove poisoning components and introduce a promoting agent into the sorbent. The method and apparatus can also be used to enhance the effectiveness of a new sorbent.
Description
Invention field
The present invention relates to remove mercury and other kind pollutant in the off-gas flows that produces in the combustion of fossil fuel process.Especially, the invention describes regenerate adsorbent of using or technology and the system that improves fresh adsorbent.
Background of invention
Combustion of fossil fuels such as coal can produce the waste gas that contains pollutant, and described pollutant comprises mercury and other trace element.In addition, contain sulphur and nitrogen oxide (sour gas discharging) and particle in the waste gas, these materials must be controlled by using adsorbent, scrubber, filter, settling vessel and other removal technology to environmental emission.With mercury is example, and the mercury that produces in the combustion process is the mercury of element morphology.The downstream of boiler, in the pipeline and chimney of combustion system, the mercury of part element morphology is oxidized.Oxidized mercury amount depends on the hydrochloric acid (HCl) that exists in the waste gas and the amount of other gas.The content of mercury is different because of the difference of coal in the air-flow, but the concentration of typical mercury is about 5/1000000000ths (ppb) in the burning gases air-flow.Therefore, in some applications, the mercury amount of discharging may be several pounds of every days.
The someone has studied the method for mercury in the polytype control waste gas, comprises injection particulate sorbent particles in the exhaust piping, makes flow through adsorbent bed of waste gas.In the method for the control mercury of these types, mercury contacts with adsorbent and is attached to its surface, and mercury can be considered the chamber or electrostatic precipitator (ESP) is assembled with flying dust at bag.A shortcoming of these prior art systems is that adsorbent can only use once, and is discarded then.Adsorbent is not regenerated and is reused.These prior aries also produce the problem of disposition of solid waste, may pollute the ash of gathering with the adsorbent of crossing, and this ash can be used for various application.
The method of another kind of control mercury is to use the carbon bed to come mercury in the capture in flue gas.In the system of these types, be typically burnedly with the adsorbent of crossing, and do not regenerate.Some prior art systems are used the cyclic carbon bed, and wherein mercury is removed with sour gas (as ammonium salt), and carbon is at high temperature regenerated, and ammonium sulfate is broken down into SO
2And N
2, mercury desorption from the adsorbent.Adsorbent attrition makes to have tangible adsorbent cost in this type control method.
The method of the control mercury of another kind of type comprises injects manganese oxide sorbent particles in off-gas flows.For example, United States Patent (USP) 6,579,507 described methods.In this patent, regeneration is to realize by washing with the oxide particle of crossing with the dilution aqueous acids from the reaction zone removal.Use a problem of manganese oxide sorbents to be, when the adsorbent oxidation and when removing in the waste gas element mercury, the speed of reaction rate much smaller than the time with active carbon.This means, compare MnO with injecting carbon adsorbent
2Adsorbent can not be handled the waste gas of high flow capacity.And, pickling MnO
2Adsorbent can not make adsorbent return to its initial activity fully.At described MnO
2In the sorbent system, the purpose of pickling processes is actually to remove with the form of dissolving salt from adsorbent surface poisons and with the manganese of mistake.This can destroy the part catalyst.Dissolving salt has polluted washing lotion, is difficult to economic separation and reclaims manganese and mercury.
The interest of design mercury control technology is to use adsorbent in particle control appliance downstream, makes adsorbent obviously do not diluted by ash particle.Adsorbent can easier regeneration and circulation then.Prior art has been discussed the example of many such structures and sorbent treatment.
U.S. Patent number 5,607,496 have described mercury oxide on the metal oxide sorbents bed, then are adsorbed onto adsorbent.Adsorbent bed is in the particle removal equipment, thereby gas still contains SO
xAnd NO
x, they and metal oxide sorbents reaction generate metal sulfate, and metal sulfate can make bed poison.The purpose of high temperature is a Regenerative beds.Yet mercury has only during up to 500 degrees centigrade part to remove from adsorbent in temperature.And adsorbent can not effectively be worked after regeneration.Reason may be that the manganese sulfate that forms in the sorption cycle process can not decompose the manganese oxide form of getting back to activity fully.United States Patent (USP) 6,383,981 describe the MnO that removes mercury from hydrocarbon stream
2Or Fe
2O
3Fixed bed, but do not comprise the method for regeneration.
United States Patent (USP) 6,596,661 have described the flat board be made up of transition metal oxide or the regeneration of cellular material, and described material is used for adsorbing the mercury of waste gas.Technology required for protection comprises that the adsorbent that adds in the thermal reduction gas stream to remove poisonous substance, then with the reagent-impregnated of the multi-functional complex compound of formation that comprises catalytic active component, recovers to catch the ability of mercury.The first step of these steps can be removed mercury, but does not know the whether actual sulfate poison of removing.Second step of these steps is very expensive, has constructed reagent again because be actually on adsorbent.
Other type uses the method for the control mercury of the porous bed that comprises the mercury oxidation reagent on the solid carrier to be used for removing mercury from air-flow, and these class methods were described in many patents.For example, United States Patent (USP) 1,984,164 have described other solid that uses active carbon or be impregnated with halogen, to remove mercury in the air.Dipping method does not have specific.Do not require regeneration.
Example comprises peroxide one sulfate (for example, United States Patent (USP) 4,786,483), and teriodide or other mix halogen (for example, United States Patent (USP) 3,194,629 and 3,662,523), and sulphur (for example, United States Patent (USP) 3,194,629; 4,101,631; 4,708,853 and 6,258,334).In these examples, reagent material or destroyed with waste gas reaction in adsorption process, perhaps destroyed in the process of attempting reproducing adsorbent.Thereby these adsorbents are not regenerated, except passing through the expensive reagent of dipping again.Can pass through microwave heating regeneration (for example, United States Patent (USP) 6,136,072) at the amalgamate noble metal (gold, silver) that is fit on the carrier, but very expensive, and in waste gas absorption, be not to have very much activity.
Summary of the invention
Remove the pollutant that accumulates on the adsorbent, the apparatus and method of the adsorbent that providing is used to regenerate used by the method that will be exposed to solution with the adsorbent of mistake.By adsorbent being exposed to the solution that improves performance of the adsorbent, the apparatus and method that improve performance of the adsorbent are also provided.In one embodiment, the solution of use is aqueous acid solution.
Other features and advantages of the present invention will embody from accompanying drawing and the following detailed description.
Summary of drawings
The present invention's method is by way of example described, and is not limited to the figure of accompanying drawing, and wherein identical Reference numeral is represented similar element, wherein:
Fig. 1 is a block diagram of describing an embodiment of sorbent regeneration technology application of the present invention.
Fig. 2 is a block diagram of describing another embodiment of sorbent regeneration technology application of the present invention.
Fig. 3 is a block diagram of describing the technology that improves performance of the adsorbent.
Describe in detail
The present invention relates to remove in the combustion of fossil fuel process, as the application of coal combustion, the technology of the mercury in the off-gas flows of generation and other kind pollutant.This is removed technology and uses adsorbent to remove pollutant in the off-gas flows, adsorbent and the interaction of other exhaust gas constituents simultaneously, described other exhaust gas constituents make adsorbent poisoning or deactivation and reduce its adsorption capacity or with the reaction rate of multiple pollutant.The present invention provides the cost of catching pollutant effective method by reactivity and the adsorption capacity of using the technology reproducing adsorbent.
Usually, technology of the present invention comprises the adsorbent that uses the reagent flushing use, selects described reagent to remove the anion of assembling in adsorbent is exposed to process in the waste gas, and described anion makes the binding site poisoning of mercury or other pollutant.Described technology is also used the reagent-impregnated adsorbent, and this reagent can promote in next life cycle of adsorbent the chemisorbed to mercury and other pollutant.The realization of this technology is by the following fact, after removing sulfate or other pollutant or in the process, washes adsorbent with recovering the reagent of adsorbent to the adsorption efficiency of mercury or other pollutant.
In certain embodiments, the present invention's be applied to regenerate adsorbent of powder type, described adsorbent injects the off-gas flows that particulate matter is removed and assembled on filter plant or ESP equipment.The example that adsorbent is formed comprises active carbon, metal oxide or multiple metal oxide, noble metal, or any their composition.In an embodiment who uses active carbon, adsorbent may be taked the form of powder, particle or fibrous carbon.Other embodiment also can.In other embodiments, adsorbent uses with adsorbent bed, rather than is injected into.Adsorbent bed can be fixed bed, fluid bed or fluidisation fabric filter.In above two kinds of any kinds, be removed from the toxic pollutant of waste gas, and add promoter and recover the mercury adsorption activity.This promotes carbon active artistic itself just and with the more expensive technology of going to adsorbent to add reagent (as peroxide, gold, teriodide etc.) to form contrast.
In order to help to understand the present invention, it is helpful understanding the ability how adsorbent lose pollutant absorption.Reaction between the acidic components that waste gas produces has been poisoned alkalescence that adsorbent is used for mercury oxide in conjunction with the position, and described mercury oxide is a lewis acid.Other metal ion also may be that the combination of the pollutant of Lewis acid will be subjected to the minimizing of inherent carbon basic sites and loses as boron, tin, arsenic, gallium, Sb, Pb, Bi, Cd, Ag, Cu, Zn or other.
Alkaline contaminant species in conjunction with the position is necessary on the adsorbent in order to obtain regeneration effect, to remove to occupy.Typically, these that have that several acidic materials occupy are in conjunction with the mercury ion quantity of position far more than combination.To being sulfuric acid in conjunction with the most serious competitor in position, described sulfuric acid is formed at the SO in the waste gas
2And SO
3The sulfate that sulfuric acid and the reaction of alkaline adsorption potential form can be by washing with aqueous hydrochloric acid (HCl) or excess chlorine ion, and exchange sulfate or disulfate ion come to remove from adsorbent.More effective with acid or flushed than the water flushing, because anion exchange is combined in the sulfate of adsorption potential.Other acid or reagent also may exchange these ions.With hydrochloric acid and/or other acid flushing also have promotion when the adsorbent reuse subsequently to the oxidation of element mercury.Form carbocation from the alkaline carbene position protonation of acid on the carbon marginal texture, this carbocation is accepted the electronics from neutral mercury atom, and described mercury atom forms the mercury oxide material and is attached to adsorbent surface.
Having multiple solution can be used for the present invention regenerates and/or improves adsorbent.In first embodiment, solution comprises one or more inorganic acids, example hydrochloric acid (HCl), hydrobromic acid (HBr) and hydroiodic acid (HI).In another embodiment, solution comprises one or more salting liquids.Salting liquid can comprise halide salt, contains relevant cation, as ammonium, sodium, potassium, iron, aluminium, boron, zinc, manganese, magnesium, calcium.In another embodiment, solution comprises organic acid, as citric acid, tartaric acid, oxalic acid, malonic acid, maleic acid, formic acid and acetic acid.In another embodiment, solution comprises organic slat solution.Organic slat solution may comprise at least one anion, described anion is from citric acid, tartaric acid, oxalic acid, malonic acid, maleic acid, formic acid and the acetic acid at least one, the cation relevant with at least one is as ammonium, sodium, potassium, iron, aluminium, boron, zinc, manganese, magnesium or calcium.
In another embodiment, solution comprises the compound of being made up of halogen and V family or VI family element such as phosphorus, oxygen, sulphur, selenium, nitrogen etc.In one embodiment, compound comprises one or more in thionyl (two) chlorine, sulfonic acid chloride, phosphorus trichloride, phosphorus oxychloride, hypochlorous acid and the chlorine.In another embodiment, compound comprises one or more in thionyl (two) bromine, sulfonic acid bromide, phosphorus tribromide, bromine phosphorous oxide, hypobromous acid and the bromine.
In another embodiment, can wash many sulfuric acid and sulfate down from carbon adsorbent for water.Yet, if carrying out preliminary treatment with halogen acids (HX) or the preceding in the carbon regeneration cycle process, halogen has been attached in the carbon, so this processing can only to recover adsorbent capturing element mercury active just effectively.
The present invention can also be included in powder sorbent or the bed material that flushing is reclaimed in the solution of pollutant removal agent, for example sour reagent of described pollutant removal agent.Wash sulfate ion and other pollutant that will exchange from the combination position of adsorbent from waste gas with the pollutant removal agent.The present invention also comprises with the reagent-impregnated adsorbent to promote adsorption activity.This can be by using promoter such as proton halogen acids HX or Lewis acid MeX
nRealize.These reagent attract mercury atom and absorb electronics from described mercury atom to improve redox active metal by produce cationic characteristic on the carbon marginal texture.The similarly oxidation of the mechanism arsenic that is applied to reduce and other polluter and catching.In another embodiment, the present invention can use the reagent that comes accelerating oxidation by the chlorination adsorbent surface, as SOCl
2, SO
2Cl
2, PCl
3, POCl
3, HOCl, NaOCl, Cl
2With corresponding bromide (or other halide) reagent.These reagent can be liquid, gas or solution reagent, depend on their stability.
The absorbent particles slurry of handling offers the dehydration method of centrifugal, gravity or filtration (for example, based on) and remove absorbent particles from aqueous acids.At last, before returning use, adsorbent is further dry by gentle heat treatment.The adsorbent dehydration has many reasons.By improving flow behavior, this step makes Powdered or the easier processing in the pipeline injection process or in osculating element of flow particles adsorbent.Moisture also may block pore, hinders the gas phase diffusion of element mercury, maybe may promote SO
2Absorption and SO subsequently
2Be oxidized to sulfuric acid.
In another embodiment, the water that dehydration produces can be handled with Ca or Mg salt in sedimentation basin, produces insoluble CaSO
4Or MgSO
4, or the not dissolved salt of other pollutant, these salt are removed as mud or solid.The Ca that is fit to or the example of Mg salt comprise lime, halide or from the solution of using of resin regeneration step.Treated water can also further be handled with the cationic ion-exchange resin of proton form, removes from any excessive Ca or Mg in the water of sedimentation basin, and replaces with hydrogen ion.Then, the solution that obtains meets the requirement (exchange out pollutant and add promoter acid) of carbon regeneration step substantially.In this technology, from the cationic ion-exchange resin Bronsted acid of using of this technology,, handle as HCl, renewable is the resin of proton form, and produces the Ca or the Mg salt of dissolving.This technology can comprise Ca and Mg salt solution from the resin regeneration unit are added to precipitation vessel, comes insoluble pollutant Ca of aids precipitation or Mg salt.This technology can also comprise, adds acid or salt as required in from the recirculated water of resin treatment step, concentration is increased to the affiliated concentration of pollutant removal and promotion adsorbent activity.
In another embodiment, from the waste water solution of dehydration can be simply by dosing in the scrubber slurry (if any), or use other disposal methods.As the purpose of design of scrubber, this will make pollutant be converted into insoluble calcium salt.
In one embodiment of the invention, before reproducing adsorbent is injected into off-gas flows, can the adsorbent of regeneration or improvement be improved by using additive to mix with adsorbent.In one embodiment, additive can be a calcium based additives, and its function is neutralizing acid.
Though the technology of the adsorbent of regeneration of deactivated is suitable for the adsorbent of various ways, below provide the specific embodiment of the regeneration technology that (comprises test result) according to the present invention.In this embodiment, use activated carbon adsorbent.Measured the regeneration of multiple carbon adsorbent, comprised Powdered Norit FGD adsorbent, aeroge carbon film adsorbent and the carbon filter that constitutes by the fine-grained carbon particle that is embedded on the polymer fiber matrix.
Carbon adsorbent begins to measure in adding hott bed, contains element mercury (11 μ g./m
3) synthetic off-gas flows by this bed.Total and concentration element mercury are measured by using the PSI continuous Launch Control Monitor of SirGalahad mercury (CEM) in the waste gas.In the test process, powder sorbent is carried by Guartz filter, and other adsorbent is measured with three times of thick layers.More original FGD powder formed carbon adsorbent and by 0.1N HBr flushing by centrifugal agglomerated powder, drying then, the adsorbent of regeneration, the result shows that the mercury capture ability is increased to 100% capture ability from about 50% capture rate of initial inlet.Relatively adsorbent showed with HBr regeneration after the life cycle once more in the second time, and the mercury capture ability when the test beginning still is 100%, and can keep higher capture rate in considerable time.Carbon film and carbon fiber absorption agent with 0.1N HCl regeneration obtain similar result.
Fig. 1 is an embodiment block diagram of the application of explanation sorbent regeneration technology of the present invention.It is restrictive that Fig. 1 should not be considered to, but describe an example system in conjunction with this technology.
The technology of Fig. 1 explanation is launched around adsorbent reactivation and treatment process 10, and under the simplest situation (as a minimum), sorbent material contacts with moisture chemical reagent.This step can also comprise that stronger stirring or abrading-ball are to expose unsalted surface.Fresh adsorbent and dose from the storage warehouse 12 and 14 that separates with the adsorbent of crossing, and with the speed metering depends on to control from the mercury of the waste gas of handling and feeds back.Contact reactor is accepted fresh adsorbent and with the mixture of the adsorbent of crossing, and is beneficial to adsorbent reactivation and treatment process 10.In one embodiment, mixture comprises adsorbent and the 20% fresh adsorbent that about 80% usefulness is crossed.Certainly, also can use other ratio.In one embodiment, be reproduced with the adsorbent of crossing and do not need to use fresh adsorbent.In contact reactor, adsorbent mixtures is exposed to and recovers the adsorbent the used adsorption efficiency to mercury in the aqueous acid solution, as mentioned above.Behind adsorbent reactivation and treatment process 10, the slurry that obtains to remove sorbent particles by initial dewatering process 16 (for example, by hydrocyclone, vacuum filtration, precipitation vessel, heat exchanger or miscellaneous equipment) from aqueous acid solution.What follow after the dewatering process 16 is final drying process 18, and its degree of using thermal process gas to make reproducing adsorbent reach obvious drying allows subsequently processing and injection to be used for the powder model system that mercury is controlled.Major part is sent regeneration reactor (by the path shown in the arrow 20) from the aqueous solution of dewatering process 16 back to compensation current 22, and described compensation current is made up of water and fresh chemical reagent.Partially aqueous solution 24 also sends back to system 26, and this system is by dosing lime and ion-exchange (by ion-exchanger 30) removes sulfate in precipitation vessel 28 before reuse.For some application, may be more prone to simple discharge currents from economic considerations and increase use fresh aqueous chemical reagent (as described below) to replace sulfate removal step.In another embodiment, as dehydration and dry replacement scheme, wet adsorbent may be annotated gets back to waste gas stream, and wet adsorbent is almost just dry immediately in air-flow.
Fig. 2 is another embodiment of the application of explanation sorbent regeneration technology of the present invention.Fig. 2 is similar to block diagram shown in Figure 1, has only very little difference.At first, Fig. 2 has provided ash content from system 32, and it can isolate flying dust from the adsorbent with mistake.
Identical with block diagram shown in Figure 1, Fig. 2 has provided storage warehouse 12 and 14, and it is used for providing fresh and with the adsorbent of crossing to contact reactor.Contact reactor is accepted fresh and with the mixture of the adsorbent of mistake, and is beneficial to adsorbent reactivation and treatment process 10.Behind adsorbent reactivation and treatment process 10, the slurry that obtains is by dewatering process 16 and drying process 18.Part is sent regeneration reactor (by the path shown in the arrow 20) from the aqueous solution of dewatering process 16 back to compensation current 22, as mentioned above.Partially aqueous solution 24 also sends back to system 26, and this system is by dosing lime and ion-exchange (by ion-exchanger 30) removes sulfate in precipitation vessel 28 before reuse.As mentioned above, for some application, may be more prone to simple discharge air-flow (" option A " shown in Fig. 2) from economic considerations and increase use the fresh aqueous chemical reagent to replace sulfate removal step 34.
The present invention also is incorporated in the efficient of improving novel sorbents.Fig. 3 has illustrated the block diagram of the efficient that is used to improve adsorbent.Fig. 3 is similar to Fig. 2, but not used adsorbent source.Fig. 3 has provided the storage warehouse 12 that is used for providing fresh adsorbent to contact reactor.Contact reactor receives fresh adsorbent, and is beneficial to sorbent treatment technology 10, and this technology will improve the efficient of adsorbent.The remainder of Fig. 3 is identical with Fig. 2.
In the detailed description in front, the present invention illustrates with reference to wherein specific exemplary embodiment.The of the present invention bigger spirit and scope that can make different modifications and change and not depart from claim and displayed.Thereby specification and accompanying drawing can be counted as illustrative, and do not have limited significance.
Claims (69)
1. the method for the adsorbent used of regeneration comprises
Generation contains the adsorbent of useful mistake and the adsorbent mixtures of unworn adsorbent;
Adsorbent mixtures is exposed to solution gathers pollutant on the adsorbent of using with removal, to recover the mercury adsorption efficiency of adsorbent;
Adsorbent mixtures is dewatered come from solution, to remove absorbent particles; With
The adsorbent mixtures of drying and dehydrating.
2. the method for claim 1 was wherein separated ash from the adsorbent of using before adsorbent mixtures is exposed to solution.
3. the method for claim 1, wherein solution comprises inorganic acid solution.
4. method as claimed in claim 3, inorganic acid solution comprise hydrochloric acid (HCl), at least a in hydrobromic acid (HBr) and the hydroiodic acid (HI).
5. the method for claim 1, wherein solution solution is salting liquid.
6. method as claimed in claim 5, salting liquid comprises halide salts, contains relevant cation, as ammonium, sodium, potassium, iron, aluminium, boron, zinc, manganese, magnesium, calcium.
7. the method for claim 1, wherein solution comprises organic acid.
8. method as claimed in claim 7, organic acid soln comprise at least a in citric acid, tartaric acid, oxalic acid, malonic acid, maleic acid, formic acid and the acetic acid.
9. the method for claim 1, wherein solution comprises organic slat solution.
10. method as claimed in claim 9, wherein organic slat solution comprises:
At least one anion, described anion is from citric acid, tartaric acid, oxalic acid, malonic acid, maleic acid, formic acid and the acetic acid at least one; With
The cation that at least one is relevant is as ammonium, sodium, potassium, iron, aluminium, boron, zinc, manganese, magnesium or calcium.
11. the method for claim 1, wherein solution only contains water.
12. the method for claim 1, the adsorbent of wherein using contains the composition from off-gas flows.
13. the method for claim 1, wherein adsorbent is an activated carbon.
14. the method for claim 1, wherein pollutant comprises sulfuric acid.
15. the method for claim 1, wherein the mercury adsorption efficiency of adsorbent can accumulate in the anion on the adsorbent of crossing by removal and recover.
16. the method for claim 1, wherein the mercury adsorption efficiency of adsorbent recovers by removing sulfuric acid from adsorbent.
17. the method for claim 1 further comprises stirring and adsorbing agent composition and solution.
18. the method for claim 1 further is included in and injects reproducing adsorbent before the off-gas flows, additive package and reproducing adsorbent.
19. method as claimed in claim 18, wherein additive neutralizing acid.
20. method as claimed in claim 18, wherein additive is a calcium based additives.
21. the method for the adsorbent that regeneration was used comprises:
To be exposed to solution with the adsorbent of crossing and gather pollutant on the adsorbent of use with removal, with the mercury adsorption efficiency of recovery adsorbent;
Adsorbent is dewatered come from solution, to remove absorbent particles; With
The adsorbent mixtures of drying and dehydrating.
22. method as claimed in claim 21, wherein solution comprises inorganic acid solution.
23. method as claimed in claim 21, wherein solution is salting liquid.
24. method as claimed in claim 21, wherein solution comprises organic acid.
25. method as claimed in claim 21, wherein solution comprises organic slat solution.
26. method as claimed in claim 21, wherein adsorbent is an active carbon.
27. the method for the adsorbent that regeneration was used comprises:
Generation contains the adsorbent of useful mistake and the adsorbent mixtures of unworn adsorbent;
Gather pollutant on the adsorbent of using with removal by adsorbent mixtures being exposed to solution, with the regenerate adsorbent of this usefulness mistake of the mercury adsorption efficiency that recovers adsorbent; With
Reproducing adsorbent is exposed to off-gas flows.
28. method as claimed in claim 27 wherein by reproducing adsorbent is injected into off-gas flows, makes reproducing adsorbent be exposed to off-gas flows.
29. method as claimed in claim 27 wherein uses fixed bed of sorbent to make reproducing adsorbent be exposed to off-gas flows.
30. method as claimed in claim 27 wherein uses fluidized bed of adsorbent to make reproducing adsorbent be exposed to off-gas flows.
31. method as claimed in claim 27 wherein uses the fluidisation fabric filter to make reproducing adsorbent be exposed to off-gas flows.
32. method as claimed in claim 27, wherein solution comprises inorganic acid solution.
33. method as claimed in claim 27, wherein solution is salting liquid.
34. method as claimed in claim 27, wherein solution is organic acid.
35. method as claimed in claim 27, wherein solution comprises organic slat solution.
36. method as claimed in claim 27, wherein adsorbent is an activated carbon.
37. improve the method for performance of the adsorbent, comprising:
Adsorbent is exposed to the solution that improves performance of the adsorbent;
Adsorbent is dewatered come from solution, to remove absorbent particles; With
The adsorbent of drying and dehydrating.
38. method as claimed in claim 37, wherein solution comprises inorganic acid solution.
39. method as claimed in claim 37, wherein solution is salting liquid.
40. method as claimed in claim 37, wherein solution comprises organic acid.
41. method as claimed in claim 37, wherein solution comprises organic slat solution.
42. method as claimed in claim 37, wherein adsorbent is an activated carbon.
43 improve the method for performance of the adsorbent, comprising:
Improve adsorbent by adsorbent being exposed to the solution that improves performance of the adsorbent; With
The adsorbent that improves is exposed to off-gas flows.
44. method as claimed in claim 43 wherein is injected into off-gas flows by the adsorbent that will improve, and makes to improve adsorbent and be exposed to off-gas flows.
45. method as claimed in claim 43 wherein uses fixed bed of sorbent to make the adsorbent of improvement be exposed to off-gas flows.
46. method as claimed in claim 43 wherein uses fluidized bed of adsorbent to make the adsorbent of improvement be exposed to off-gas flows.
47. method as claimed in claim 43 wherein uses the fluidisation fabric filter to make the adsorbent of improvement be exposed to off-gas flows.
48. method as claimed in claim 43, wherein solution comprises inorganic acid solution.
49. method as claimed in claim 43, wherein solution is salting liquid.
50. method as claimed in claim 43, wherein solution comprises organic acid.
51. method as claimed in claim 43, wherein solution comprises organic slat solution.
52. method as claimed in claim 43, wherein solution comprises by halogen and combines the compound of forming with V family or VI family element.
53. method as claimed in claim 52, wherein compound comprises one or more in thionyl (two) chlorine, sulfonic acid chloride, phosphorus trichloride, phosphorus oxychloride, hypochlorous acid and the chlorine.
54. method as claimed in claim 52, wherein compound comprises one or more in thionyl (two) bromine, sulfonic acid bromide, phosphorus tribromide, bromine phosphorous oxide, hypobromous acid and the bromine.
55. method as claimed in claim 43, wherein adsorbent is an activated carbon.
56. the mercury in the removal combustion of fossil fuels process in the off-gas flows or the method for other pollutant comprise:
Adsorbent is exposed to off-gas flows to remove the pollutant in the off-gas flows;
To mix with fresh adsorbent with the adsorbent of crossing, and mixture is exposed to solution gathers pollutant on the adsorbent of using with removal, with the mercury adsorption efficiency of recovery adsorbent;
Mixture is dewatered come from solution, to remove absorbent particles;
Dry sorbent particles; With
The sorbent particles of drying is exposed to off-gas flows to remove the extra pollutant in the off-gas flows.
57. method as claimed in claim 56, wherein adsorbent is an activated carbon.
58. method as claimed in claim 56, wherein solution comprises inorganic acid solution.
59. method as claimed in claim 56, wherein solution is salting liquid.
60. method as claimed in claim 56, wherein solution comprises organic acid.
61. method as claimed in claim 56, wherein solution comprises organic slat solution.
62. the device of reproducing adsorbent comprises:
Be used to receive and comprise the contact reactor of the mixture of the adsorbent used and unworn adsorbent, wherein, the mixture in the contact reactor is exposed to aqueous acid solution and recovers the adsorption efficiency of adsorbent to mercury;
Be used for removing the dehydration equipment of the absorbent particles of aqueous acid solution; With
The drier of dry absorbent particles.
63. device as claimed in claim 62, wherein contact reactor further comprises the method that one or more stir the mixture.
64. device as claimed in claim 62, wherein dehydration equipment is made up of hydrocyclone.
65. device as claimed in claim 62, wherein dehydration equipment is made up of precipitation vessel or thickener.
66. device as claimed in claim 62, wherein dehydration equipment is made up of filter plant.
67. device as claimed in claim 62, wherein drier is made up of heat exchanger.
68. device as claimed in claim 62, wherein drier is made up of fluidising chamber.
69. device as claimed in claim 62 further comprises adsorbent ash separator, it is used for separating the adsorbent of using from ash before being received by contact reactor.
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| US46486803P | 2003-04-23 | 2003-04-23 | |
| US60/464,868 | 2003-04-23 | ||
| PCT/US2004/012828 WO2004094024A2 (en) | 2003-04-23 | 2004-04-23 | Process for regenerating a spent sorbent |
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| EP (1) | EP1624963B1 (en) |
| CN (1) | CN1826175B (en) |
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| PL (1) | PL1624963T3 (en) |
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| CN103648636A (en) * | 2011-08-15 | 2014-03-19 | 英派尔科技开发有限公司 | Oxalate sorbents for mercury removal |
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| CN111518600B (en) * | 2019-12-23 | 2021-05-18 | 新疆中宇金盾碳基研究院(有限公司) | Saltpetering inhibitor, semi-coke type carbon containing saltpetering inhibitor and preparation method thereof |
| CN112717904A (en) * | 2020-12-28 | 2021-04-30 | 宜宾丝丽雅股份有限公司 | Recovery process method of resin activator by bipolar membrane pretreatment process |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2004094024A2 (en) | 2004-11-04 |
| EP1624963B1 (en) | 2019-11-27 |
| PL1624963T3 (en) | 2020-05-18 |
| US20120202679A1 (en) | 2012-08-09 |
| PT1624963T (en) | 2020-01-07 |
| EP1624963A2 (en) | 2006-02-15 |
| US20070167309A1 (en) | 2007-07-19 |
| WO2004094024A3 (en) | 2004-12-16 |
| CN1826175B (en) | 2015-07-01 |
| EP1624963A4 (en) | 2011-10-05 |
| US8440585B2 (en) | 2013-05-14 |
| CA2523132C (en) | 2012-06-05 |
| US8173566B2 (en) | 2012-05-08 |
| CA2523132A1 (en) | 2004-11-04 |
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